Azo dyestuffs and process of making same



Patented Mar. 26, 1929.

WERNER ZERWECK, 0F FECHENHEIM, NEAR RRANKROR'r-ON-THR MAIN, GERMANY,

.ASSIGNOR T0 GRASSELLI DYESTUFF CORPORATION, OF NEW PORATION OF DELAWARE.

YORK, N. Y., A COR AZO DYESTUFFS AND PROCESS OF MAKTNG SAME.

No Drawing. Application filed November 15, 1926, Serial No. 148,620, and in Germany November 17, 1925.

The invention relates to new azo dyestufis and a process of making the same, said dyestuffs having probably the general formula:

alryl alryl i? f [N Ii on H0 0 O-NH-R=X-R1NHO 0 wherein X represents the triazolic group '.N\ I N or the ditriazolic groups L Nary1-aryl-N I Band B, represent aryl residues of the group including the benzene and naphthalene series which in addition to the amino group may be further substituted. The'new dyestuffs may be obtained by combining any diazo compound not containing a sulfonic acid group with a derivative of 2.3-hydroxynaphthoic acid of the general formula:

wherein X, R and R have the same definition as above.

These derivatives of 2.3-hydroxynaphthoic' The aminotriazolic compounds may be obtained for instance by oxidizing correspondingly substituted ortho-amino-azo bodies.

The new dyestuffs yield valuable color lakes, whenmlxed with the usual substrata, they are particularly adapted for being produced on the vegetable fiber, because the derivatives of 2.3-hydroxynaphthoic acid of the above-said formula are distinguished by an especial aflinity to the vegetable fiber. It is therefore not necessary to dehydrate the padded dyed goods as far as possible by squeezing, pressing or centrifuging prior to developing, it is sufficientto treat the padded dyed goods in moist condition with the usual rinsing solution. The dyeings, obtained by developing With various diazosolutions, range from yellowish to black and possess a remarkable brightness and intensity and, owing to the substantive character of the used azocomponent, an especial fastness to rubbing.

In order to further illustrate my inven tion the following example is given, the parts being by weight and all temperatures in centigrade degrees, but it is understood that my" invention is not limited to the particular products or reaction conditions mentioned therein. Example.

Cotton yarn, which has been well boiled and dried, is impregnated with a solution of '10 grams of the di-2.3-hydroxynaphthoylcompound of 5-amino-2- para-aminophenyl) 1.3-benzotriazol, 17 c. c. of caustic soda solution of 34 B. and-25 c. c. of Turkey red oil per liter, wellwrung out, rinsed and, Without being dried, developed with a diazosolution, neutralized with a solution of sodium acetate and containing 3 grams of 3-nitro- 1.4-toluidin' per liter.

The dyestufi", thus produced on the fiber, has probably the formula:

easily soluble in dilute hydrochloric acid and forms a difiicultly soluble sulfate.

If instead of the di-2-3-hydroxynaphthoyl compound of the named tria-zol derivative that of the 5-amino-2-(meta-aminophenyl)- manner from m-aminoacetanilide). is used for the process, a brilliant scarlet red is obtained, when combined with diazotized 3- Iiitro-lA-toluidin, and a brilliant bluish red, when combined with diazotized para-chloroortho-toluidin.

The new dyestuffs may also be produced by printing a diazosolution on a padded material according to the usual method or also according to the nitrosamin printing process.

In the same manner the process may be conducted with other diazo-, tetrazoor polyazo bodies and the 2.3-1iydroxynaphthoyl compounds of other triazolic derhatives.

The following table gives the shades ob tained on cotton material by producing some r' 1.3-benzotriazol (obtainable in an analogous other dyestuffs according to my process Two molecular proportions of the diazocolnpound or one Combinedwith the di-2.3-hydroxynaphthoyl-derivatives Sh d molecular proportion of the tetrazocompound 01- a c 3-nitro-L4-toluidin 5- mino-2-(m-amino-phenyl-) 1.3-benz-triaz0l Bluish red. p-nitranilin Scarlet. 4-nitro-L2-toluidin I Yellowish red. 5-nitro-L2-anisidin. Claret red.

- Diamino-diphenyl-methane Bluish black.

o-methoxy-benzolazo-mnaph Violet black. 3-nitro1.4-to1uidin Bluish red. p-nitranilin Scarlet. 4-nitro-L2-toluidin. Yellowish red. diaminodiphenyl-methane Bluish black. o-methoxy-benzolazo-a-naphthylamine. Bluish violet-black. 3-nitro-L4-toluidin 5 ammo 6 methyl -2- (4-methyl 5 ammo phenyl) Bluish red.

- 1.3-benztriazol. p-nitranilin. do Scarlet. -nitro-LHoluidin- I d Yellowish red. m-nitranilin 5-sm1no-6- methyl-2-(4-methyl-5-amino-phenyl) 1.3- Orange.

. benztriazol. 5-nitro-L2-anisidin... do Claret rod. 4-nitro-L2-anisidin. do Red. Diamino-diphenylamine do Bluish black. o-methoxy-benzolazo-a-nephthylamine do Black. 3-nitro-1.4-to1uidin 5-amino-4-methyl-2-(m-amino-phenyl) l.3-benztriazol. Red. p-nitranilin do Scarlet. 4-nitro-L2-toluidin. do Yellowish red. Diamino-diphenyl-methane. do Bluish black. o-methoxy-benzolazo-q-naphthylamine d Dark black. 3nitro-L4 tolu1d1n 5-amino-6chlor-2-(m-aminophenyl) 1.3benztriazol Brilliant red. p-nitranilim do Brilliant scarlet. 4-nitro-l.2-toluidin do Yellowish ml. p-chlor-o-fnlnidin Marc ing-em?boxy-2-(3'-amino-4-mcthoxy-phenyl) 1.3- Brilliant red.

DZ 8Z0 p-chlor-o-toluidin 5-amino-6-methoxy-2-(2'-methyl-4-amino-5-mctlloxy- Bluish rod,

' phenyl)-1.3-benztriazol.

H: Black.

Diamincvdiphenyl-amine HzN N H OCHa OCHa I Black. Diamino-diphenyl-amine Hi0 III-4i -N--I]IONH2 BIN N N H|CO 1 OCH; 0CHa p-nitranilin HzN NN NH: Brownish red.

The dyestufi' resulting from the combinadiazo compound of p-chlor-o-toluidine with tion of two molecular proportions of'the the di-2.3-hydroxynaphthoyl derivative of 5-amino-6 methoxy-2 (3-amino-l'-methoxyphenyl)-1.3-benztriazol has the following I claim:

1. As new comp probable formula:

ounds the unsulfonated Aryl H N I in which formula X represents the triazolic group or the ditriazolic group andR and R represent aryl residues of the group including the benzene and naphtha lene series which in addition to the amino group may be further substituted, yielding upon reduction with stannous chloride an arylamin (two molecular proportions) and the corresponding derivative of the l-amino- 2-hydroxylnaphthalene-3-carboxyamide, being adapted for the production of valuable color'la-kes, when mixed with the usual substrata, and yielding when produced on the Vegetable fiber dyeings of a remarkable brightness and intensity and an excellent fastness, especially to rubbing.

2. The process of making new azodyestuifs which comprises combining any aromatic diazocompound,' not containing a sulfonic group, with a derivative of 2.3-hydroxynaphthoic acid of the general formula:

OH HO in which formula X represents the triazolic group or the ditriazolic group and R and R represent aryl residues of the group including the benzene and naphthalene series which in addition to the amino group may be further substituted.

3. The process of producing new azodyestufis onthe vegetable fiber which comprises impregnating the fiber with a derivative of 2.3-hydroxynaphthoic acid of the general formula:

in which formula X represents the triazolic group or the ditriazolic group and R and R represent aryl residues of the group including the benzene and naphthalene series which in addition 'to the amino group may be further substituted, and developing then with any aromatic diazocompound, not containing a sulfo'nic group.

4. Materials dyed with the new azodyestuffs of claim 1, said dyestufi's being pro- (luced on the fiber of the material.

wherein R represents a benzene nucleus which may be substituted by halogen, alkyl, alkoxy or nitro, and Z represents hydrogen or methyl.

wherein R represents a benzene nucleus which may be substituted by halogen, alkyl, alkoxy or nitro.

7. Materials dyed with the new azodyestuffs of claim 5, said dyestuffs being produced on the fiber of the material.

wherein R and R represent nuclei of the benzene or naphthalene series which may be substituted by halogen, alkyl or alkoxy and R represents a nucleus of the benzene or napththalene series which may be substituted by halogen, alkyl, alkoxy or nitro.

6. As new compounds the unsulfonated and uncarboxylated azodyestufl's of the general formula:

OCH:

8. Materials dyed with the new azodyestufis of claim 6, said dyestufi's being produced on the fiber of the material.

9. As new compounds the unsulfonated and uncarboxylated azodyestuifs of the general formula: 1

10. As new compounds the unsulfonated and uncarboxylated azodyestuifs of the general formula:

wherein R represents a benzene nucleus which may be substitutedby halogen, alkyl, alkoxy or nitro and one of the Ys represents halogen, alkyl or alkoXy and the other Y represents hydrogen.

11. Materials dyed with the new azodyestufls of claim 9, said dyestuff being produced on the fiber of thematerial.

12. Materials dyed with the new vazodyestufl's of claim 10, said dyestufi being produced on the fiber of the material.

In testimony whereof, I aflix my signature.

WERNER ZERWECK.

CERTIFICATE OF CORRECTION.

Patent No. 1,706,946. Granted March 26, 1929, to

' WERNER ZERWECK.

It is hereby certified that error appears in the printed specification of the above-numbered patent requiring correction as follows: Page 4. lines 37 and 38, for "Y represents" read "Y s represent": and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed, this 23rd day of April, A. D. 1929.

M. J. Moore, (Seal) Acting Commissioner of Patents.

GERTIFZCATE OF GORRECTMN.

Patent No. 1,706,946. Granted March 26, 1929, to

WERNER ZERWECK.

it is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 4-, lines 37 and 38,

for "Y represents" read "Ys represent"; and that. the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the ?atent Office.

Signed and sealed this 23rd day of April, A. D. 1929.

M. J. Moore, (Seal) Actirig Commissioner of Patents. 

